Intramolecular Anodic Olefin Coupling Reactions

通过这个奖项，有机化学和高分子化学项目支持了华盛顿大学教授凯文·D·默勒的研究。本研究项目研究分子内阳极烯烃偶联反应，在该反应中，碳-碳键的形成提供了保留官能团手柄的环状产物，以供进一步的合成精制。Moeller教授正在利用这种反应性来合成角度稠合的三喹烷和相关的5-6-5-稠环体系(蒜素A)。类似的烯烃-杂原子偶联提供了通往吡咯环的途径，导致了免疫抑制剂FR901483的合成。通过手性烯酸酯类化合物的氧化和随后产生的自由基阳离子的亲核捕获，Moeller教授寻求不对称偶联反应，而其他研究则涉及分子间烷基化反应中的极性反转和开发新的氧化途径来获得杂环。碳-碳键的形成是合成复杂有机分子最关键的要求之一，Moeller教授正在开发新的方法来实现这一点。在他的方法中，碳-碳键的形成动力是通过从选定的反应物中去除电子来提供的。尽管这样的氧化反应通常会受到各种化学氧化剂的影响，但默勒教授利用了电化学技术，使用像6伏灯笼电池这样简单的设备来进行所需的转化。

With this award, the Organic and Macromolecular Chemistry Program supports the research of Professor Kevin D. Moeller of Washington University. This research project studies intramolecular anodic olefin coupling reactions, in which carbon-carbon bond formation occurs to afford cyclic products which retain functional group handles for further synthetic elaboration. Professor Moeller is exploiting this reactivity for the synthesis of angularly-fused triquinanes and related 5-6-5-fused ring systems (alliacol A). Analogous olefin-heteroatom couplings offer access to pyrrolidine rings, leading to synthesis of the immunosuppressant FR901483. Through the oxidation of chiral enolate equivalents and subsequent nucleophilic trapping of the resulting radical cations, Professor Moeller seeks asymmetric coupling reactions, while other studies address the reversal of polarity in intermolecular alkylation reactions and the development of new oxidative routes to heterocycles.Formation of carbon-carbon bonds represents one of the most critical requirements for the synthesis of complex organic molecules, and Professor Moeller is developing new methods to accomplish this. In his method, the driving force for carbon-carbon bond formation is provided by the removal of electrons from selected reactants. Although such oxidation reactions are often effected by a variety of chemical oxidants, Professor Moeller exploits electrochemical techniques, using equipment as simple as a 6-Volt lantern battery to carry out the desired transformations.